微波辐照气相法合成氮掺杂石墨烯

以天然鳞片石墨为原料, 采用Staudenmaier法先制备出石墨氧化物, 再经饱和碳酸铵溶液浸渍后生成NH₄⁺插层石墨氧化物. 在微波照射下, NH₄⁺分解生成的NH₃与剥离的石墨烯氧化物反应原位合成出氮掺杂石墨烯. 通过SEM、TEM、EDS、XRD、XPS和Raman测试手段对氮掺杂石墨烯进行了表征. 结果表明, 所合成的氮掺杂石墨烯呈透明绢丝状结构, 每个石墨烯片含有2~5层石墨层; 氮元素含量为1.56wt%, 其中N元素是以pyridinc N、 pyrrolic N和graphitic N形式掺入石墨层网格中.     

氮掺杂和SnO2纳米粒子负载对全固态对称型石墨烯超级电容器性能的影响

电极材料是影响超级电容器性能的主要因素。本研究采用溶剂热法合成石墨烯和氮掺杂石墨烯, 通过简单的化学法在其表面负载SnO₂纳米粒子。利用刮涂工艺在FTO玻璃表面制备石墨烯、SnO₂/石墨烯、氮掺杂石墨烯和SnO₂/氮掺杂石墨烯薄膜, 并经400℃热处理。分别以制备的石墨烯基薄膜和PVA/H₃PO₄为电极和电解质组装对称型全固态超级电容器。测试结果表明, 与石墨烯相比, 氮掺杂石墨烯具有较大的晶粒尺寸、较高的比表面积和较高的超电容性能; SnO₂纳米粒子负载可显著提高石墨烯和氮掺杂石墨烯的超电容性能。     

活化和氮掺杂炭层包覆碳纳米管载铂催化剂电催化性能研究

利用化学浸渍还原法,以原始和混酸活化碳纳米管,及聚苯胺改性制备的氮掺杂炭层包覆碳纳米管为载体,制备上述碳纳米管负载铂催化剂,研究比较它们作为质子交换膜燃料电池催化剂的电催化性能。透射电镜观察表明,以混酸活化碳纳米管为载体一定程度改善了铂粒子在碳管上的沉积形态和分散性,沉积的铂粒子大小约5~8nm,但铂粒子仍存在较明显的团聚现象;而因聚苯胺改性碳纳米管外层为均匀氮掺杂炭层,铂粒子能均匀分散沉积于氮掺杂层表面,其平均粒径约为2~4nm。电化学分析表明,混酸活化和氮掺杂炭层包覆碳纳米管都能够改善负载催化剂的电催化活性,尤其氮掺杂炭层包覆碳纳米管负载铂催化剂不仅具有最高氧还原活性,其负载催化剂同时展现了良好的循环稳定性。     

氮掺杂碳纳米管的制备及其应用

氮掺杂可以调控碳纳米管的电子结构及表面性质,以吡啶氮、吡咯氮(N-5)、石墨氮、氧化吡啶、-NO2及-NH2等形式进行掺杂的含氮官能团可提高碳纳米管的氧还原催化活性、赝电容、润湿性能及供电子特性。文章综述氮掺杂碳纳米管的3种制备方法:同步原位掺杂、碳化含氮物质、后处理,及其在氧还原反应、超级电容器和支撑材料方面的应用,并综述了不同种类含氮官能团的作用。     

氮掺杂炭层包覆碳纳米管的组织结构调控及其氧还原催化活性

采用化学原位聚合合成聚吡咯涂覆碳纳米管,之后将其在氮气氛下热处理制备氮掺杂炭层包覆碳纳米管NCCNTs。利用该工艺,通过改变热处理温度,调控NC-CNTs组织结构和表面化学组成。比表面和孔结构分析显示,600,800和1 000℃热处理制备的氮掺杂碳纳米管NC-CNT600,NC-CNT800和NC-CNT1000的比表面积和孔体积依次显著增加,NC-CNT1000的比表面积和孔体积分别约是NC-CNT600的3倍和1.7倍。这是因碳纳米管表面聚吡咯层向氮掺杂炭层转化过程导致更多的微孔形成。然而,制备温度升高使NC-CNTs的氮含量降低,表面含氮官能团由吡咯型氮向吡啶型氮和石墨氮转化,NC-CNT1000含最高比例的石墨氮。作为无金属催化剂,NC-CNTs在碱性电解质条件下展现了明显的氧还原催化活性,但其氧还原活性并不与样品氮含量成正比。NC-CNT600和NC-CNT800的氧还原反应为两电子转移机制,而NCCNT1000表现为两电子和四电子转移混合机制,其展现出最高的氧还原催化活性和催化稳定性,这可能是其具有高的比表面积和孔体积,结合含氮官能团中高比例石墨氮的缘故。     

氮/硫共掺杂对纤水镁石模板碳纳米管电化学性能的影响

以天然矿物纤水镁石为模板、蔗糖为碳源制备多孔碳纳米管, 并以硫脲为氮、硫源, 采用水热法制备氮/硫共掺杂的碳纳米管。结果表明, 掺杂碳纳米管继承了纤水镁石模板的柱状结构, 呈现中空管状, 增大了模板炭的比表面积和孔容。在6 mol·L^-1 KOH电解液中, 电流密度为1 A·g^-1时, 未掺杂碳纳米管的比电容为62.2 F·g^-1, 氮掺杂之后碳纳米管的比电容为97.0 F·g^-1, 氮/硫共掺杂的碳纳米管比电容为172.0 F·g^-1, 氮/硫共掺杂后碳纳米管的电化学性能比未掺杂的提高近3倍; 循环1000次电容保持率达89%, 说明掺/硫共掺杂碳纳米管具有良好的电化学性能。此外, 组装的对称型超级电容器同样展示了良好的电容性能。     

铁氮共掺杂介孔碳材料的简易制备及其氧还原反应催化性能

氧还原反应(ORR)是燃料电池阴极重要的电化学反应过程,其自发反应进程缓慢,对氧还原反应起高效催化作用的催化剂面临价格昂贵、合成流程复杂、污染环境等问题,因此探索合成简单、环境友好的氧还原催化剂制备方法具有重要意义。铁氮共掺杂介孔碳材料(Fe-N/MC)是一种有巨大应用价值的非贵金属氧还原反应催化剂。本工作通过在马弗炉中的半封闭体系内高温碳化小分子前驱体得到介孔碳材料(MC_M),再把获得的MC_M与铁盐混合在管式炉中高温处理制备得到铁氮共掺杂介孔碳材料(Fe-N/MC_MT)。该方法热解条件简单,无需模板剂和NH₃、HF等有毒物质。由于MC_M含有较高的氮和氧元素,有利于提升介孔碳材料表面的亲水性和配位能力,通过MC_M和铁盐制备出的Fe-N/MC_MT含有丰富的、催化ORR的Fe-N_x活性位点,其起始电位和半波电位分别为0.941和0.831 V(vs RHE),比商业化Pt/C催化剂的起始电位和半波电位分别正34和16...     

PMDA-ODA型聚酰亚胺炭/碳纳米管杂化膜的制备及气体分离性能研究

针对现有气体分离炭膜存在的渗透速率低等问题, 提出并设计在PMDA-ODA型聚酰亚胺前驱体中掺杂碳纳米管, 经高温热解后制备炭/碳纳米管杂化膜. 分别采用透射电镜(TEM)、X射线衍射分析(XRD)和气体渗透实验对炭/碳纳米管杂化膜的微观结构和分离性能进行表征. 实验结果表明, 在PMDA-ODA型聚酰亚胺前驱体中掺杂碳纳米管后, 碳纳米管与炭基体之间形成明显的“界面间隙”, 打破了原有炭膜中由乱层炭构成的无序微孔结构, 重新构建了杂化炭膜的孔隙结构. 与纯炭膜相比, 杂化炭膜的气体渗透速率大幅增加, 其中O₂的渗透速率增大接近4倍(达到1576 Barrer), 而O₂/N₂的分离选择性仅降低17%.     

纳米管协同碳纳米管导电纸对石墨负极性能的影响

以碳纳米管(Multi-walled carbon nanotubes)为导电剂,协同以碳纳米管和纸纤维复合成的CNTs导电纸为集流体,对石墨负极进行电化学改性。石墨化处理碳纳米管作为负极的添加相,采用XRD、SEM和TGA对其分析。结果表明,对比单纯的石墨/铜箔负极,掺杂0.8%(质量分数)石墨化碳纳米管的石墨/铜箔负极,电池比容量由304mAh/g变为308mAh/g,相差不大,但循环效率由86%升至92%;使用CNTs导电纸做集流体时,掺杂0.8%(质量分数)石墨化碳纳米管的石墨/CNTs导电纸负极,比容量由308mAh/g升至401mAh/g,提高30%,循环效率由92%升至95%,提高3%。说明碳纳米管协同CNTs导电纸对石墨负极具有积极的改性意义。     

具有增强类过氧化物酶活性的硼掺杂石墨氮化碳负载单原子铁催化剂（英文）

开发具有高活性的生物医药和环保催化剂是目前的研究热点.本文中,我们通过三聚氰胺与氧化硼混合搅拌后热解而获得硼掺杂石墨相氮化碳(B-g-C₃N₄).通过离子交换后热解的方式制备了硼掺杂石墨氮化碳上负载Fe单原子的纳米酶(SA Fe/B-g-C₃N₄).同步辐射和扫描透射电子显微镜研究表明单原子Fe催化剂被成功制备.得到的SA Fe/B-gC₃N₄在H₂O₂存在下能够表现出良好的类过氧化物酶活性.同时,密度泛函理论计算进一步验证了B掺杂对催化反应的促进作用.基于这些发现,我们利用SA Fe/B-g-C₃N₄构建了一个比色传感器,用于检测硫化物阴离子的浓度,其检测限为0.57μmol L^-1.本方法对自来水和海水中的S^2-检测被验证真实可靠.     

Biocompatibility and toxicological studies of carbon nanotubes doped with nitrogen

In this report, we compare the toxicological effects between pure carbon multiwalled nanotubes (MWNTs) and N-doped multiwalled carbon (CNx) nanotubes. Different doses of tubes were administered in various ways to mice: nasal, oral, intratracheal, and intraperitoneal. We have found that when MWNTs were injected into the mice's trachea, the mice could die by dyspnea depending on the MWNTs doses. However, CNx nanotubes never caused the death of any mouse. We always found that CNx nanotubes were far more tolerated by the mice when compared to MWNTs. Extremely high concentrations of CNx nanotubes administrated directly into the mice's trachea only induced granulomatous inflammatory responses. Importantly, all other routes of administration did not induce signs of distress or tissue changes on any treated mouse. We therefore believe that CNx nanotubes are less harmful than MWNTs or SWNTs and might be more advantageous for bioapplications.     

碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

碳纤维表面原位固相协同生长纳米碳管

在碳纤维(CF)表面直接原位生长碳纳米管(CNTs),可有效避免CNTs分散不均的问题,充分发挥二者的优势,对获得高层间性能的碳纤维增强树脂基复合材料(CNTs-CF/EP)具有重要的意义。本文对CF进行表面改性处理,在CF表面负载催化剂粒子,然后通过原位生长法并在助催化剂噻吩的协同作用下,在CF表面固相生长了CNTs。此方法得到的CNTs-CF,不仅有效避免CNTs在基体中的相互缠绕、难以分散等问题。而且由于生长CNTs的碳源主要来自CF,二者结合强度较高,对提高CNTs-CF/EP的层间性能非常有利。借助于SEM、XRD及FT-IR等分析测试手段,研究了催化剂Ni(NO_3)_2·6H_2O浓度对表面长有CNTs的CF的形貌、结构及其性能的影响。结果表明:在适当的催化剂浓度(0.2mol·L~(-1))负载中,CF表面能够生长出结合牢固、垂直生长且均匀分布的CNTs,但力学性能有所下降。     

Growth of carbon nanotubes on cobalt catalyst film using electron cyclotron resonance chemical vapour deposition without thermal heating

This paper demonstrates that carbon nanotubes (CNTs) can be synthesized on a cobalt coated silicon substrate using electron cyclotron chemical vapour deposition and without intentionally heating the substrate. With the mixed gases of C(3)H(8)/N(2), CNTs with a multi-walled structure and a diameter up to 70?nm have been observed. Results show that the diameter of the CNTs increases with the thickness of the cobalt catalyst film and the amount of nitrogen incorporated in the CNT films considerably influences the structures of the CNTs. Vertically aligned CNTs can be fabricated with a microwave power as low as 300?W and the flow rate ratio of C(3)H(8)/N(2) = 20/20?sccm. The CNTs exhibit a turn-on field of 0.2?V?μm(-1) determined at the emission current density of 10?μA?cm(-2).     

Synthesis of carbon nanotubes on metal mesh in inverse diffusion biofuel flames

In this study, renewable biofuels (ethanol and n-butanol) were utilized to synthesize carbon nanotubes on substrate of inexpensive metal mesh (copper alloy and nickel) using inverse diffusion flame. The effects of metal mesh, synthesis time and flame temperature on growth of carbon nanotubes (CNTs) were investigated in details. The morphology and structure of CNTs were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The results showed that there were no CNTs formed on nickel mesh. When the substrate was copper alloy mesh, the yield of CNTs increased from 2?min and reached maximum at about 15?min as the synthesis time increased. Under the condition of 15?min, CNTs synthesized in ethanol flame of 1023?K and in n-butanol flame of 1273?K had higher degree of graphitic structure. In addition, multi-walled carbon nanotubes (MWCNTs) with straight tube wall were synthesized in ethanol flame of 1023?K and 1273?K when the synthesis time was 15?min. For these experiments, CNTs with excellent quality could be synthesized effectively in ethanol flame with temperatures of 1023?K and 1273?K when the synthesis time was 15?min and the substrate was copper alloy mesh.     

Grafting of polystyrene on nitrogen-doped multi-walled carbon nanotubes

Polymer grafting of polystyrene (PS) on nitrogen-doped multiwall carbon nanotubes (CNx) was successfully obtained by a "grafting from" technique. The production method involves the immobilization of initiators, using wet chemistry, onto the nanotube surface, followed by an in situ surface-initiated polymerization. The polymer-grafting carbon nanotubes synthesis includes the free radical functionalization of CNx and the "controlled/living" Nitroxide Mediated Radical Polymerization (NMRP). The obtained products were studied using several microscopic techniques as scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and electron energy loss spectroscopy (EELS). The characterization also includes thermogravimetric analysis (TGA), Raman spectroscopy, infrared spectroscopy, and electron spin resonance (ESR), among others. The analyzed samples were also compared with solutions fabricated by physical blending of the polymer and CNx nanotubes. These results indicate that the nanotube radical functionalization, the chemical grafting, and the polymerization reaction were obtained over CNx when NMRP method was successfully used, giving rise to a uniform PS layer of several nanometers grafted on the outer surface of the CNx nanotubes. Several properties of the PS-grafted CNx nanotubes were also studied. It is shown that the production method leads to a narrower distribution of the external diameters. Moreover, their solubilization in organic solvents is greatly improved. Finally, the dispersion of PS-grafted CNx into a PS matrix is studied to determine the differences in filler dispersion and interfacial adhesion strength, in comparison with nanocomposites elaborated with as-produced CNx.     

Effect of carbon nanotubes on the mechanical properties and crystallization behavior of poly(ether ether ketone)

Pristine carbon nanotubes (CNTs) and noncovalently functionalized carbon nanotubes (f-CNTs) were used to prepare poly(ether ether ketone) (PEEK) composites (CNTs/PEEK and f-CNTs/PEEK) via melt blending. Noncovalently functionalized multiwalled nanotubes were synthesized using hydrogen-bonding interactions between sulfonic groups of sulfonated poly(ether ether ketone) (SPEEK) and carboxylic groups of nanotubes treated by acid (CNTs–COOH). The effects of these two kinds of nanotubes on the mechanical properties and crystallization behavior of PEEK were investigated. CNTs improved mechanical properties and promoted the crystallization rate of PEEK as a result of heterogeneous nucleation. Better enhancement of mechanical properties appeared in the f-CNTs/PEEK composites, which is ascribed to the good interaction between f-CNTs and PEEK. However, the strong interaction of f-CNTs and PEEK chains decreased the crystallization rate of PEEK for high content of f-CNTs.     

Synthesis of nano-carbon (nanotubes,nanofibres, graphene) materials

In the present study, we report the synthesis of carbon nanotubes (CNTs) using a new natural precursor: castor oil. The CNTs were synthesized by spray pyrolysis of castor oil-ferrocene solution at 850°C under an Ar atmosphere. We also report the synthesis of carbon nitrogen (C-N) nanotubes using castor oil-ferrocene-ammonia precursor. The as-grown CNTs and C-N nanotubes were characterized through scanning and transmission electron microscopic techniques. Graphitic nanofibres (GNFs) were synthesized by thermal decomposition of acetylene (C₂H₂) gas using Ni catalyst at 600°C. As-grown GNFs reveal both planar and helical morphology. We have investigated the structural and electrical properties of multi-walled CNTs (MWNTs)-polymer (polyacrylamide (PAM)) composites. The MWNTs-PAM composites were prepared using as purified, with ball milling and functionalized MWNTs by solution cast technique and characterized through SEM. A comparative study has been made on the electrical property of these MWNTs-PAM composites with different MWNTs loadings. It is shown that the ball milling and functionalization of MWNTs improves the dispersion of MWNTs into the polymer matrix. Enhanced electrical conductivity was observed for the MWNTs-PAM composites. Graphene samples were prepared by thermal exfoliation of graphite oxide. XRD analysis confirms the formation of graphene.     

Effect of fuel structure on synthesis of carbon nanotubes in diffusion flames

Carbon nanotubes (CNTs) were synthesized on nickel nitrate coated nickel foam in co-flow diffusion flames. Two different fuel structures, methane and ethylene, were used to synthesize CNTs. The effect of fuel structure on CNTs was systematically studied. Results showed that carbon nanomaterials, including nanotubes and nanofibers, were successfully synthesized in all conditions in methane flames, while, in ethylene flames, bamboo-like CNTs were synthesized in limited conditions. It was also found that carbon nanomaterials synthesized in ethylene flames had more defects than that of in methane flames. In addition, metal nickel nanoparticles acted as catalysts in the synthesis of CNTs, and carbon nanomaterials diameter was dependent on the catalyst particle size. Flame-synthesized CNTs were based on the vapor-liquid-solid mechanism, and a “recursive growth mechanism” for CNTs growth was proposed, which would be more conducive to the understanding of CNTs growth mechanism. This method offers another possibility for low-cost, large-scale synthesis of carbon nanomaterials.     

定向碳纳米管的化学气相沉积制备法

报道了一种简便有效的合成定向碳纳米管 (CNTs)的化学气相沉积 (CVD)制备方法。以铁为催化剂 ,乙炔为碳源 ,采用单一反应炉 ,直接在石英基底上沉积催化剂颗粒薄膜 ,成功合成了定向性好、管径均匀的高质量大密度的碳纳米管